Winfrid hentrich and max habdtmann



Patented 'Nov. 17, 1931 UNITED, STATES raraur OFFICE WINFRID HENTRIOH AND MAX HARDTMANTT, OF WmSDORF-ON-TH E-RHINE, AND

HEINRICH METZL, OF LEVMUSEN-ON-THE-BHINE GERMANY, ASSIGNOBS TO GENERAL ANILI'NE WORKS, 1110., OF NEW YORK, N. Y. A- CORPORATION 01 DELA- WARE nmnc AND rnmrme or rnxrrnn nmnns no Drawing. Application mean rn a, 1929, serial 110. 858,670, and in Germany April 30, 1928.

The present inventionrelates to a process of dyeing textile fibers by slop-padding and printing.

The printingand slop-padding of textile fibers with the esters of the leuco-compounds of vat dyestuffs, such as indigo, indigoid dyestuifs, anthraquinone dyestuffs andothers (compare British Patent 186,057) is performed by printing or slop-padding the fibers in the usual manner with a printing paste or in a bath respectivel containing a leuco-ester of said vat dyestufi s, an agent for saponifying the ester, an oxidizing agent, such as sodium chlorate, an oxidizing catalyst, such as v the ammonium salt of the vanadinic or tungstic-acid and, in the case of printing, thickening agent, for example starch, gum or tragacanth. The fiber which has been printed or slop-padded in the usual manneris dried, then the dyestuffs is developed by saponification of the ester and oxidation of the leuco- :omp ound,.finally thefiber is rinsed and dried.

Heretofore the developing of the, dyestuif, that means the saponification of the ester and oxidation of the leuco-compound, has been performed by the catalytical action of hydrogen ions which were produced the developing process from the saponifymg agent present in the printinglpaste 'or slop-paddm bath respectively by t 0 interaction of stea during a short time say for about 5-10 utes. It is self-evident that only such sapomfying substances can be used as do not unfavorably influence the fiber and .the dyestufi'. Heretofore water-soluble rhodanides have been used generally as saponifymg agents, es-

- pecially ammonium rhodan1de;. but these rhodanides are liable to change the tints of sensitive dyestufls. In order to overcome this disadvantage, dieth I-tartrate has beenused instead of the rh anides, but the tartaric acid being a very weak acid, a great quantity of this compound, 6% and more calculated onfthe amount of the print ng paste or the slop-padding bath, is necessary.

'TAccording .to the present invention, there are added to the printing paste or slop-paddingbath as saponifyin'g agents, that means as agents yieldin hydrogen ions by the ac- ,tion of steam, c orides, esters and anhyvmay be varied within drides, of aliphatic and aromatici sulfom'c acids and of aromatic carboxylic acids, the sulfo-chlorides of the aromatic series being the most valuable'saponifying agents. The quantity of the ne'wsaponifying agents used the widest limits; enerally we add to the printing paste or ath about 1 to about 8% or more calculated on the amount of the printing paste or bath; but,.

when applyinga high percentage of the'sao pomfying agents, care must be taken that the fiber is not damaged, As the saponifying agents used in our invention are insoluble in water, they are added to the paste or bath dissolved-in a suitable organic solvent, such as diethylenedioxide, acetone, alcohol, d -(B- hydroxyethyl) -thioether, enerally in a conylester of naphthalene-2-sulfonic acid naphthalene-1.6-disulfochloride and the esters of the naphthalene-1.6-disulfonic acid, naphthalene-2l7-disulfochloride, and the esters of the naphthalene-2.7-disulfonic acid, naphthalene 1.3.6 trisulfochloride. The latter compound does react somewhat more slowly than the other ones and therefore the developing process takes more time than usual; the 4-methylbenzene-1-sulfochloride and the esters of the correspondin sulfonic acids rea'ct still more slowly. uitable compounds are fui'ther *terephthaloylchloride reacting more rapidly than the above mentioned compounds, benzene-l-carboxylic acid chloride-- 3-sulfochloride, 2-naphthoic-acid chloride and B-chloro-ethane-sulfochlorid The saponifying agents used in our inwention are very stable, even in admixture with the printing paste, and therefore a premature developing of the d estuflz does not occur. On the other hand, w on treating the printed ester of the leuco-compound of 4.4-dimethyltreated for about.5 minutes with saturated 6.6'-dichloro-'thioindigo, 30 parts by weight of water, 45 parts by weight of a neutral starch tragacanth thickening agent (consisting of 10% of wheat starch, 10% of water and80% of a 6% tragacanth slime), 1 part by weight of sodium'chlorate dissolved in 2 parts y weight of water, 1,25 parts by weight of naphthalene-1.G-disulfochloride dissolved in di- (,B-hydroxyethyl) -thioether and 10 parts by weight of an aqueous solution of the ammonium salt of vanadinic acid dissolved 1:1000). The print is dried,

steam, soaped on the boil and dried.

For the purpose of our invention the"slop padding process is an equivalent of the printm process.

1. The process which comprises printing fibers with a printing paste containing an ester of a leuco-compound of a vat dyestufl,

an oxidizing agent, an oxidizing catalyst, a thickening agent and a saponifymg agent of the group consisting of the chlorides, esters and anhydrides of aliphatic sulfonic acids and of sulfonic and carboxylic acids of the benzene and naphthalene series, drying the fibers, steaming, washing and drying the 2. The lprocess which comprises printing fibers wit a printing paste containing an ester of a'leuco-compound of a vat dyestufi, an oxidizing agent, an oxidizing catalyst, a th ckening agent and an aromatic sulfochloride of the benzene and naphthalene ser es, the fibers, steaming, washing and drlyl'mg't e same.

3. T e process which comprises printing fiberswith a printing paste containing an ester of a leuco-compound of a vat dyestufi',

an oxidizing agent, an oxidizing catalyst, a thickening agent and na hthalene-L6-disu'lfochloride, drying the fibers, steaming, washing and drying the same. 4 4. The process which comprises" printing fibers with a printing paste containing an ester of a leuco-compound of a vat dyestufi', an oxidizing agent, an oxidizing catalyst, a thickening agent and about l'to 8%- (calculated on the weight of the printing paste) of a saponifying agent of the group consisting of the chlorides, esters and anhydrides of aliphatic sulfonic acidsand of sulfonic and carboxylic acids 'of the benzene and naphthalene series dryin the fibers, steaming,

and drying e same.

. 5. T e process which comprises printing 6. The process which comprises printing fibers with a printing paste containing an ester of a leuco-compound of a vat dyestufi, an oxidizing agent, an oxidizing catalyst, a thickening agent and. Ito 8% (calculated on the weight of the printing paste) of naphthalene-1.6-disulfochloride, drying the fibers, steaming, washing and drying the same;

7. The process which comprises printing fibers with a printing paste containing an ester of a leuco-compound of a vat dyestufi, an oxidizing agent, an oxidizing catalyst, a thickening agent and about 1,25% (calculated on the weight of the printing paste) of a sa'ponifying agent of the group consisting of the chlorides, esters and anhydrides of aliphatic sulfonic acids and of sulfonic and carboxylic acids of the benzene and naphthalene series, drying the fibers, steaming, washing and drying the same.

8. The process which comprises printing fibers with a printing paste containing an ester of a leuco-compound of a vat dyestufi, an oxidizing agent, an oxidizing catalyst, a thickening agent and about 1,25% (calculated on the weight of the printing paste) of an aromatic sulfochloride of the benzene and naphthalene series, drying the fibers,

steaming, washing and drying the same.

9. The process which comprises printing. fibers with a printing paste containing an ester of a leuco-compound of a vat dyestufi', an oxidizing agent, an oxidizing catalyst, a thickening agent and about 1,25% (calculated 'on the weight of the printing paste) of naphthalene-1.fi-disulfochloride, 'drying the fibers, steaming, washing and drying the same.

10. The process which comprises printing fibers with a printigg paste containin a sulfuric acid ester of a leuco-compound 0 an indigoid dyestuff, sodium chlorate, ammonium salt of vanadinic acid, a thickening agent and'about 1,25% (calculated on the weight of the printing paste) of a saponifying agent of the group consisting of the 'chlorides, esters and anhfydrides of aliphatlc sulfonic acids and of sul onic and carboxyl-ic acids of the benzene and naphthalene series,

drying the fibers, steaming, washing and drying the same. 11. The process which comprises printing fibers with a printing paste containing a sulfuric acid ester of a leuco-compound of an indigoid dyestufi, sodium chlorate, ammonium salt of vanadinic acid, a thickening agent and about 1,25% (calculated on the weight of the printing paste) of an aromatic sulfochloride of the benzene and naphthalene series, drying the fibers, steaming, washing and drying the same.

12. The process which comprises printing fibers with a printing aste containing a sulfuricacid ester of a fiance-compound of an indigoid dyestuif, sodium chlorate, ammonium salt of vanadinio acid, a thickening agent'and about 1,25% (calculated on the weight of the printing paste) of naphthalene- LG-disulfochloride, drying the fibers, steaming, washing and drying the same.

In testimony whereof we have hereunto set our hands.

WINF-RID HENTRICH. [L.s;] MAX HARDTMANN. HEINRICH METZL. 

